US20040138489A1 - Composition and method for low temperature deposition of silicon-containing films - Google Patents

Composition and method for low temperature deposition of silicon-containing films Download PDF

Info

Publication number
US20040138489A1
US20040138489A1 US10/699,079 US69907903A US2004138489A1 US 20040138489 A1 US20040138489 A1 US 20040138489A1 US 69907903 A US69907903 A US 69907903A US 2004138489 A1 US2004138489 A1 US 2004138489A1
Authority
US
United States
Prior art keywords
hnbu
silicon
composition
hnme
silicon compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US10/699,079
Other versions
US7446217B2 (en
Inventor
Ziyun Wang
Chongying Xu
Thomas Baum
Bryan Hendrix
Jeffrey Roeder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Entegris Inc
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/294,431 external-priority patent/US7531679B2/en
Application filed by Individual filed Critical Individual
Priority to US10/699,079 priority Critical patent/US7446217B2/en
Priority to AU2003287710A priority patent/AU2003287710A1/en
Priority to JP2004552143A priority patent/JP2006517517A/en
Priority to EP03781915A priority patent/EP1567531A4/en
Priority to PCT/US2003/036097 priority patent/WO2004044958A2/en
Assigned to ADVANCED TECHNOLOGY MATERIALS, INC. reassignment ADVANCED TECHNOLOGY MATERIALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HENDRIX, BRYAN, BAUM, THOMAS H., ROEDER, JEFF, WANG, ZIYUN, XU, CHONGYING
Publication of US20040138489A1 publication Critical patent/US20040138489A1/en
Priority to US12/247,120 priority patent/US7713346B2/en
Publication of US7446217B2 publication Critical patent/US7446217B2/en
Application granted granted Critical
Priority to US12/777,519 priority patent/US7887883B2/en
Priority to US13/028,193 priority patent/US8236097B2/en
Assigned to GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT reassignment GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ADVANCED TECHNOLOGY MATERIALS, INC., ATMI PACKAGING, INC., ATMI, INC., ENTEGRIS, INC., POCO GRAPHITE, INC.
Assigned to GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT reassignment GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ADVANCED TECHNOLOGY MATERIALS, INC., ATMI PACKAGING, INC., ATMI, INC., ENTEGRIS, INC., POCO GRAPHITE, INC.
Assigned to ENTEGRIS, INC. reassignment ENTEGRIS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ADVANCED TECHNOLOGY MATERIALS, INC.
Assigned to ATMI PACKAGING, INC., ENTEGRIS, INC., POCO GRAPHITE, INC., ADVANCED TECHNOLOGY MATERIALS, INC., ATMI, INC. reassignment ATMI PACKAGING, INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Assigned to POCO GRAPHITE, INC., ATMI PACKAGING, INC., ATMI, INC., ENTEGRIS, INC., ADVANCED TECHNOLOGY MATERIALS, INC. reassignment POCO GRAPHITE, INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Assigned to GOLDMAN SACHS BANK USA reassignment GOLDMAN SACHS BANK USA SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ENTEGRIS, INC., SAES PURE GAS, INC.
Assigned to MORGAN STANLEY SENIOR FUNDING, INC. reassignment MORGAN STANLEY SENIOR FUNDING, INC. ASSIGNMENT OF PATENT SECURITY INTEREST RECORDED AT REEL/FRAME 048811/0679 Assignors: GOLDMAN SACHS BANK USA
Assigned to TRUIST BANK, AS NOTES COLLATERAL AGENT reassignment TRUIST BANK, AS NOTES COLLATERAL AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CMC MATERIALS, INC., ENTEGRIS GP, INC., ENTEGRIS, INC., INTERNATIONAL TEST SOLUTIONS, LLC, POCO GRAPHITE, INC., QED TECHNOLOGIES INTERNATIONAL, INC.
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/025—Silicon compounds without C-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/308—Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/3143—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
    • H01L21/3144—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604—Deposition from a gas or vapour
    • H01L21/31608—Deposition of SiO2
    • H01L21/31612—Deposition of SiO2 on a silicon body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/318—Inorganic layers composed of nitrides
    • H01L21/3185—Inorganic layers composed of nitrides of siliconnitrides

Definitions

  • the present invention relates generally to the formation of silicon-containing films in the manufacture of semiconductor devices, and more specifically to compositions and methods for forming such films, e.g., films comprising silicon, silicon nitride (Si 3 N 4 ), siliconoxynitride (SiO x N y ), silicon dioxide (SiO 2 ), etc., low dielectric constant (k) thin silicon-containing films, high k gate silicate films and low temperature silicon epitaxial films.
  • Silicon nitride (Si 3 N 4 ) thin films are widely employed in the microelectronic industry as diffusion barriers, etch-stop layers, sidewall spacers, etc.
  • CVD precursors include bis(tert-butylamino)silane (BTBAS) or silane/ammonia, but such precursors usually require deposition temperature higher than 600° C. for forming high quality Si 3 N 4 films, which is incompatible with the next generation IC device manufacturing, where deposition temperature of below 500° C., and preferably about 450° C., is desired. Therefore, development of low-temperature silicon-containing CVD precursors is particularly desired.
  • BBAS bis(tert-butylamino)silane
  • silane/ammonia silane/ammonia
  • hexachlorodisilane Cl 3 Si—SiCl 3
  • the drawbacks of using hexachlorodisilane in CVD processes include: (i) formation of large amount of NH 4 Cl during the process, which leads to the particle contamination and solid build-up in vacuum system and exhaust lines; (ii) possible chlorine incorporation in the chips, which could significantly reduce their life time and long-term performance. It is therefore desirable to develop new chlorine-free precursors that can be used for low-temperature CVD formation of silicon nitride.
  • the present invention relates generally to the formation of silicon-containing films, such as films comprising silicon, silicon nitride (Si 3 N 4 ), siliconoxynitride (SiO x N y ), silicon dioxide (SiO 2 ), etc., silicon-containing low k films, high k gate silicates, and silicon epitaxial films, among which silicon nitride thin films are preferred, in the manufacture of semiconductor devices, and more specifically to compositions and methods for forming such silicon-containing films.
  • silicon-containing films such as films comprising silicon, silicon nitride (Si 3 N 4 ), siliconoxynitride (SiO x N y ), silicon dioxide (SiO 2 ), etc.
  • silicon-containing low k films silicon oxide
  • high k gate silicates silicon epitaxial films
  • the present invention in one aspect relates to a group of chlorine-free disilane derivatives that are fully substituted with alkylamino and/or dialkylamino functional groups and can be used as CVD precursors for deposition of silicon-containing thin films.
  • Such disilane derivative compounds can be represented by the general formula of:
  • R 1 -R 12 may be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 5 alkyl, and C 3 -C 6 cycloalkyl.
  • the disilane derivative compound of the present invention is characterized by a symmetrical structure in relation to the Si—Si bond.
  • such disilane derivative compound contains at least two alkylamino functional groups that are symmetrically distributed in relation to the Si—Si bond.
  • Such disilane derivative compound may also contain two or more dialkylamino functional groups symmetrically distributed in relation to the Si—Si bond.
  • such disilane derivative compound is selected from the group consisting of (NEt 2 ) 2 (HNMe)Si—Si(HNMe)(NEt 2 ) 2 , (HNBu t ) 2 (HNMe)Si—Si(HNMe)(HNBu t ) 2 , and (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 , wherein Et is used as the abbreviation of ethyl, Bu t is used as the abbreviation of t-butyl, and Me is used as the abbreviation of methyl, consistently throughout herein.
  • Another aspect of the present invention relates to a method for forming a silicon-containing film on a substrate, comprising contacting a substrate under chemical vapor deposition conditions including a deposition temperature of below 550° C., preferably about 500° C., with a vapor of a disilane compound that is fully substituted with alkylamino and/or dialkylamino functional groups.
  • Still another aspect of the present invention relates to a method of making (NEt 2 ) 2 (HNMe)Si—Si(HNMe)(NEt 2 ) 2 , by reacting (NEt 2 ) 2 (Cl)Si—Si(Cl)(NEt 2 ) 2 with excess H 2 NMe.
  • Yet a further aspect of the present invention relates to a method of making (HNBu t ) 2 (HNMe)Si—Si(HNMe)(HNBu t ) 2 , by reacting (HNBu t ) 2 (Cl)Si—Si(Cl)(HNBu t ) 2 with LiN(H)Me.
  • a still further aspect of the present invention relates to a method of making (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 , by reacting (HNBu t ) 2 (Cl)Si—Si(Cl)(HNBu t ) 2 with LiNH 2 .
  • a still further aspect of the present invention relates to a method of forming silicon-containing thin films on a substrate, by contacting the substrate under chemical vapor deposition conditions with a vapor of an above-described disilane derivative compound, or a mixture of two or more above-described disilane derivatives.
  • the deposition temperature is not higher than 550° C., more preferably not higher than 500° C., and most preferably not higher than 450° C.
  • FIG. 1 is a STA plot for (NEt 2 ) 2 (HNMe)Si—Si(HNMe)(NEt 2 ) 2 .
  • FIG. 2 is a STA plot for (HNBu t ) 2 (HNMe)Si—Si(HNMe)(HNBu t ) 2 .
  • FIG. 3 is a STA plot for (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 .
  • FIG. 4 is an X-ray crystal structure of the compound (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 .
  • the present invention relates to silicon precursors for CVD formation of films on substrates, such as silicon precursors for forming low k dielectric films, high k gate silicates, low temperature silicon epitaxial films, and films comprising silicon, silicon oxide, silicon oxynitride, silicon nitride, etc., as well as to corresponding processes for forming such films with such precursors.
  • Disilane derivatives that are fully substituted with alkylamino and/or dialkylamino functional groups, free of any halogen-substitutes, are found particularly suitable for low-temperature deposition of silicon nitride thin films.
  • Such fully substituted disilane compound may be represented by the generic formula of:
  • R 1 -R 12 may be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 5 alkyl, and C 3 -C 6 cycloalkyl.
  • the fully substituted disilane compounds of the above formula are advantageously characterized by a melting temperature of less than 10° C., and a vaporization temperature of less than 300° C. Moreover, such disilane compounds can be transported in vapor form at less than 300° C., with no or little ( ⁇ 1%) residual material at atmospheric pressure.
  • the silicon-containing films that can be formed using such disilane precursor compounds include low dielectric constant (k) thin films, high k gate silicates and silicon epitaxial films. In a particularly preferred embodiment of the invention, the films formed using such disilane precursors comprise silicon nitride.
  • Preferred disilane compounds of the above-described formula include those characterized by a symmetrical structure in relation to the Si—Si bond, such as (NEt 2 ) 2 (HNMe)Si—Si(HNMe)(NEt 2 ) 2 , (HNBu t ) 2 (HNMe)Si—Si(HNMe)(HNBu t ) 2 , and (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 , etc.
  • such disilane compounds contain at least two alkylamino functional groups and/or two or more dialkylamino functional groups that are symmetrically distributed in relation to the Si—Si bond.
  • both (HNBu t ) 2 (HNMe)Si—Si(HNMe)(HNBu t ) 2 and (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 contain four t-butylamino functional groups that are symmetrically distributed in relation to the Si—Si bond;
  • (NEt 2 ) 2 (HNMe)Si—Si(HNMe)(NEt 2 ) 2 contains two methylamino functional groups and four diethylamino functional groups that are symmetrically distributed in relation to the Si—Si bond.
  • FIG. 1 shows the STA plot for (NEt 2 ) 2 (HNMe)Si—Si(HNMe)(NEt 2 ) 2 , which has a melting temperature of about 81.7° C., and can be transported in its vapor form completely with almost no residual material at about 300° C. at atmospheric pressure or in a flow of inert gas.
  • FIG. 2 is the STA plot for (HNBu t ) 2 (HNMe)Si—Si(HNMe)(HNBu t ) 2 , showing an even lower melting temperature of about 34.0° C., with only 0.55% residual material when vaporized at about 250° C. at atmospheric pressure or in a flow of inert gas.
  • FIG. 3 is the STA plot for (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 , which has a melting temperature of about 72.1° C. and can be transported in its vapor form at about 250° C., with only 0.49% residual material noted at 500° C.
  • FIG. 4 further shows an X-ray crystal structure of the disilane derivative compound (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 .
  • the disilane compound (NEt 2 ) 2 (HNMe)Si—Si(HNMe)(NEt 2 ) 2 can be synthesized by reacting (NEt 2 ) 2 (Cl)Si—Si(Cl)(NEt 2 ) 2 with excess amount of H 2 NMe, according to the following equations:
  • the disilane compound (HNBu t ) 2 (HNMe)Si—Si(HNMe)(HNBu t ) 2 can be synthesized by reacting (HNBu t ) 2 (Cl)Si—Si(Cl)(HNBu t ) 2 with about 2 molar ratio of LiN(H)Me, according to the following equations:
  • the disilane compound (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 can be synthesized by reacting (HNBu t ) 2 (Cl)Si—Si(Cl)(HNBu t ) 2 with about 2 molar ratio of LiNH 2 , according to the following equations:
  • disilane derivative compounds of the present invention as described hereinabove can be used, either separately or as mixtures, for low-temperature CVD deposition of various silicon-containing films, including silicon nitride thin films, consistent with the disclosure in U.S. patent application Ser. No. 10/294,431 for “Composition and Method for Low Temperature Deposition of Silicon-Containing Films Including Silicon Nitride, Silicon Dioxide and/or Silicon-Oxynitride” filed on Nov. 14, 2002, the content of which is incorporated by reference in its entirety for all purposes.
  • one or more of the above-described disilane derivatives are first dissolved in a hydrocarbon solvent or a solvent system that comprises at least one hydrocarbon solvent.
  • Suitable hydrocarbon solvents for the practice of the present invention include, but are not limited to, alkylamines such as HN i Pr 2 , wherein i Pr is used herein as the abbreviation of isopropyl.
  • Such solution containing the disilane derivative(s) of the present invention is vaporized at a temperature that is not higher than 300° C., preferably not higher than 150° C., and more preferably about 120° C., and transported to the deposition chamber together with a carrier gas, such as helium or argon, for contact with a heated substrate surface to deposit the silicon-containing thin films.
  • a carrier gas such as helium or argon
  • a solution of the compound (HNEt) 3 Si—Si(HNEt) 3 was prepared at a concentration of 0.4M in a hydrocarbon solvent and at a concentration of 0.036M in HN i Pr 2 . These solutions were metered at 0.0127 ml/minute and 0.167 ml/miniute, respectively into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas. The vapor was mixed with 50 sccm or 25 sccm, respectively of NH 3 in a showerhead vaporizer device that was maintained at 120° C. and thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at 10 Torr to 60 Torr during deposition. The growth rate of the silicon nitride films ranged from 72 ⁇ /minute to 34 ⁇ /minute depending upon pressure, temperature, NH 3 rate, and precursor rate.
  • a solution of the compound of Example 1, (NEt 2 ) 2 (HNMe)Si—Si(HNMe)(NEt 2 ) 2 was prepared at a concentration of 0.4M in a hydrocarbon solvent. This solution was metered at 0.0127 ml/minute or 0.025 ml/miniute into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas. The vapor was mixed with 50 sccm or 300 sccm of NH 3 in a showerhead vaporizer device that was maintained at 120° C. and thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at 5 Torr to 60 Torr during deposition. The growth rate of the silicon nitride films ranged from 20 ⁇ /minute to 2 ⁇ /minute depending upon pressure, temperature, NH 3 rate, and precursor rate.
  • a solution of the compound of Example 2, (HNBu t ) 2 (HNMe)Si—Si(HNMe)(HNBu t ) 2 was prepared at a concentration of 0.4M in a hydrocarbon solvent. This solution was metered at 0.0127 ml/minute or 0.025 ml/miniute into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas. The vapor was mixed with 50 sccm or 300 sccm of NH 3 in a showerhead vaporizer device that was maintained at 120° C.
  • the chamber pressure was maintained at 20 Torr to 60 Torr during deposition.
  • the growth rate of the silicon nitride films ranged from 30 ⁇ /minute to 2 ⁇ /minute depending upon pressure, temperature, NH 3 rate, and precursor rate.
  • a solution of the compound of Example 3, (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 was prepared at a concentration of 0.4M in a hydrocarbon solvent and at a concentration of 0.072M in HN i Pr 2 . These solutions were metered at 0.0127 ml/minute or 0.025 ml/miniute or 0.05 ml/minute or 0.07 ml/minute into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas.
  • sccm standard cubic centimeters per minute
  • the vapor was mixed with 38 sccm to 300 sccm of NH3 in a showerhead vaporizer device that was maintained at 120° C. and thereby dispersed over the surface of a heated Si(100) wafer.
  • the chamber pressure was maintained at 4 Torr to 60 Torr during deposition.
  • the growth rate of the silicon nitride films ranged from 68 ⁇ /minute to 7 ⁇ /minute depending upon pressure, temperature, NH 3 rate, and precursor rate.
  • a solution of two compounds: 0.0576M (HNBu t ) 2 (NH 2 )Si—Si(NH 2 )(HNBu t ) 2 , 0.0144M (HNEt) 3 Si—Si(HNEt) 3 was prepared in HN i Pr 2 .
  • This solution was metered at 0.0138 ml/minute into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas.
  • the vapor was mixed with 275 sccm of NH 3 in a showerhead vaporizer device that was maintained at 120° C.
  • the chamber pressure was maintained at 10 Torr to 60 Torr during deposition.
  • the growth rate of the silicon nitride films ranged from 33 ⁇ /minute to 7 ⁇ /minute depending upon pressure and temperature.

Abstract

This invention relates to silicon precursor compositions for forming silicon-containing films by low temperature (e.g., <300° C.) chemical vapor deposition processes for fabrication of ULSI devices and device structures. Such silicon precursor compositions comprise at least one disilane derivative compound that is fully substituted with alkylamino and/or dialkylamino functional groups.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This is a continuation-in-part of U.S. patent application Ser. No. 10/294,413 filed Nov. 14, 2002 in the names of Ziyun Wang, Chongying Xu, Ravi K. Laxman, Thomas H. Baum, Bryan C. Hendrix, and Jeffrey F. Roeder.[0001]
    • FIELD OF THE INVENTION
  • The present invention relates generally to the formation of silicon-containing films in the manufacture of semiconductor devices, and more specifically to compositions and methods for forming such films, e.g., films comprising silicon, silicon nitride (Si[0002] 3N4), siliconoxynitride (SiOxNy), silicon dioxide (SiO2), etc., low dielectric constant (k) thin silicon-containing films, high k gate silicate films and low temperature silicon epitaxial films.
    • DESCRIPTION OF THE RELATED ART
  • Silicon nitride (Si[0003] 3N4) thin films are widely employed in the microelectronic industry as diffusion barriers, etch-stop layers, sidewall spacers, etc.
  • Deposition of silicon nitride films by chemical vapor deposition (CVD) techniques is a highly attractive methodology for forming such films. CVD precursors currently used include bis(tert-butylamino)silane (BTBAS) or silane/ammonia, but such precursors usually require deposition temperature higher than 600° C. for forming high quality Si[0004] 3N4 films, which is incompatible with the next generation IC device manufacturing, where deposition temperature of below 500° C., and preferably about 450° C., is desired. Therefore, development of low-temperature silicon-containing CVD precursors is particularly desired.
  • Presently, hexachlorodisilane, Cl[0005] 3Si—SiCl3, is being studied as a candidate precursor for low-temperature CVD formation of silicon nitride upon reaction with ammonia gas. The drawbacks of using hexachlorodisilane in CVD processes include: (i) formation of large amount of NH4Cl during the process, which leads to the particle contamination and solid build-up in vacuum system and exhaust lines; (ii) possible chlorine incorporation in the chips, which could significantly reduce their life time and long-term performance. It is therefore desirable to develop new chlorine-free precursors that can be used for low-temperature CVD formation of silicon nitride.
    • SUMMARY OF THE INVENTION
  • The present invention relates generally to the formation of silicon-containing films, such as films comprising silicon, silicon nitride (Si[0006] 3N4), siliconoxynitride (SiOxNy), silicon dioxide (SiO2), etc., silicon-containing low k films, high k gate silicates, and silicon epitaxial films, among which silicon nitride thin films are preferred, in the manufacture of semiconductor devices, and more specifically to compositions and methods for forming such silicon-containing films.
  • The present invention in one aspect relates to a group of chlorine-free disilane derivatives that are fully substituted with alkylamino and/or dialkylamino functional groups and can be used as CVD precursors for deposition of silicon-containing thin films. [0007]
  • Such disilane derivative compounds can be represented by the general formula of: [0008]
    Figure US20040138489A1-20040715-C00001
  • wherein R[0009] 1-R12 may be the same as or different from one another and each is independently selected from the group consisting of H, C1-C5 alkyl, and C3-C6 cycloalkyl.
  • Preferably, the disilane derivative compound of the present invention is characterized by a symmetrical structure in relation to the Si—Si bond. In one preferred embodiment of the present invention, such disilane derivative compound contains at least two alkylamino functional groups that are symmetrically distributed in relation to the Si—Si bond. Such disilane derivative compound may also contain two or more dialkylamino functional groups symmetrically distributed in relation to the Si—Si bond. [0010]
  • More preferably, such disilane derivative compound is selected from the group consisting of (NEt[0011] 2)2(HNMe)Si—Si(HNMe)(NEt2)2, (HNBut)2(HNMe)Si—Si(HNMe)(HNBut)2, and (HNBut)2(NH2)Si—Si(NH2)(HNBut)2, wherein Et is used as the abbreviation of ethyl, But is used as the abbreviation of t-butyl, and Me is used as the abbreviation of methyl, consistently throughout herein.
  • Another aspect of the present invention relates to a method for forming a silicon-containing film on a substrate, comprising contacting a substrate under chemical vapor deposition conditions including a deposition temperature of below 550° C., preferably about 500° C., with a vapor of a disilane compound that is fully substituted with alkylamino and/or dialkylamino functional groups. [0012]
  • Still another aspect of the present invention relates to a method of making (NEt[0013] 2)2(HNMe)Si—Si(HNMe)(NEt2)2, by reacting (NEt2)2(Cl)Si—Si(Cl)(NEt2)2 with excess H2NMe.
  • Yet a further aspect of the present invention relates to a method of making (HNBu[0014] t)2(HNMe)Si—Si(HNMe)(HNBut)2, by reacting (HNBut)2(Cl)Si—Si(Cl)(HNBut)2 with LiN(H)Me.
  • A still further aspect of the present invention relates to a method of making (HNBu[0015] t)2(NH2)Si—Si(NH2)(HNBut)2, by reacting (HNBut)2(Cl)Si—Si(Cl)(HNBut)2 with LiNH2.
  • A still further aspect of the present invention relates to a method of forming silicon-containing thin films on a substrate, by contacting the substrate under chemical vapor deposition conditions with a vapor of an above-described disilane derivative compound, or a mixture of two or more above-described disilane derivatives. Preferably, the deposition temperature is not higher than 550° C., more preferably not higher than 500° C., and most preferably not higher than 450° C. [0016]
  • Other aspects, features and embodiments of the invention will be more fully apparent from the ensuing disclosure and appended claims.[0017]
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a STA plot for (NEt[0018] 2)2(HNMe)Si—Si(HNMe)(NEt2)2.
  • FIG. 2 is a STA plot for (HNBu[0019] t)2(HNMe)Si—Si(HNMe)(HNBut)2.
  • FIG. 3 is a STA plot for (HNBu[0020] t)2(NH2)Si—Si(NH2)(HNBut)2.
  • FIG. 4 is an X-ray crystal structure of the compound (HNBu[0021] t)2(NH2)Si—Si(NH2)(HNBut)2.
    • DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS THEREOF
  • The present invention relates to silicon precursors for CVD formation of films on substrates, such as silicon precursors for forming low k dielectric films, high k gate silicates, low temperature silicon epitaxial films, and films comprising silicon, silicon oxide, silicon oxynitride, silicon nitride, etc., as well as to corresponding processes for forming such films with such precursors. [0022]
  • Disilane derivatives that are fully substituted with alkylamino and/or dialkylamino functional groups, free of any halogen-substitutes, are found particularly suitable for low-temperature deposition of silicon nitride thin films. [0023]
  • Such fully substituted disilane compound may be represented by the generic formula of: [0024]
    Figure US20040138489A1-20040715-C00002
  • wherein R[0025] 1-R12 may be the same as or different from one another and each is independently selected from the group consisting of H, C1-C5 alkyl, and C3-C6 cycloalkyl.
  • The fully substituted disilane compounds of the above formula are advantageously characterized by a melting temperature of less than 10° C., and a vaporization temperature of less than 300° C. Moreover, such disilane compounds can be transported in vapor form at less than 300° C., with no or little (≦1%) residual material at atmospheric pressure. The silicon-containing films that can be formed using such disilane precursor compounds include low dielectric constant (k) thin films, high k gate silicates and silicon epitaxial films. In a particularly preferred embodiment of the invention, the films formed using such disilane precursors comprise silicon nitride. [0026]
  • Preferred disilane compounds of the above-described formula include those characterized by a symmetrical structure in relation to the Si—Si bond, such as (NEt[0027] 2)2(HNMe)Si—Si(HNMe)(NEt2)2, (HNBut)2(HNMe)Si—Si(HNMe)(HNBut)2, and (HNBut)2(NH2)Si—Si(NH2)(HNBut)2, etc. More preferably, such disilane compounds contain at least two alkylamino functional groups and/or two or more dialkylamino functional groups that are symmetrically distributed in relation to the Si—Si bond. For example, both (HNBut)2(HNMe)Si—Si(HNMe)(HNBut)2 and (HNBut)2(NH2)Si—Si(NH2)(HNBut)2 contain four t-butylamino functional groups that are symmetrically distributed in relation to the Si—Si bond; (NEt2)2(HNMe)Si—Si(HNMe)(NEt2)2 contains two methylamino functional groups and four diethylamino functional groups that are symmetrically distributed in relation to the Si—Si bond.
  • FIG. 1 shows the STA plot for (NEt[0028] 2)2(HNMe)Si—Si(HNMe)(NEt2)2, which has a melting temperature of about 81.7° C., and can be transported in its vapor form completely with almost no residual material at about 300° C. at atmospheric pressure or in a flow of inert gas.
  • FIG. 2 is the STA plot for (HNBu[0029] t)2(HNMe)Si—Si(HNMe)(HNBut)2, showing an even lower melting temperature of about 34.0° C., with only 0.55% residual material when vaporized at about 250° C. at atmospheric pressure or in a flow of inert gas.
  • FIG. 3 is the STA plot for (HNBu[0030] t)2(NH2)Si—Si(NH2)(HNBut)2, which has a melting temperature of about 72.1° C. and can be transported in its vapor form at about 250° C., with only 0.49% residual material noted at 500° C.
  • FIG. 4 further shows an X-ray crystal structure of the disilane derivative compound (HNBu[0031] t)2(NH2)Si—Si(NH2)(HNBut)2.
  • Synthesis of several preferred disilane derivatives is described in the following examples: [0032]
    • EXAMPLE 1 Synthesis of (NEt2)2(HNMe)Si—Si(HNMe)(NEt2)2
  • The disilane compound (NEt[0033] 2)2(HNMe)Si—Si(HNMe)(NEt2)2 can be synthesized by reacting (NEt2)2(Cl)Si—Si(Cl)(NEt2)2 with excess amount of H2NMe, according to the following equations:
  • (NEt2)2(Cl)Si—Si(Cl)(NEt2)2+excess H2NMe→(NEt2)2(HNMe)Si—Si(HNMe)(NEt2)2+2H2NMe·HCl
  • Specifically, a 1 L flask was filled with a solution comprising 500 mL diethyl ether and 20 grams (48.2 mmol) of (NEt[0034] 2)2(Cl)Si—Si(Cl)(NEt2)2. H2NMe was bubbled into such solution. White precipitate was observed during the addition of H2NMe. Approximately 20 grams of H2NMe (644.25 mmol) was added into the 1 L reaction flask during a ten-hour period. The resulting mixture was filtered, and all volatile materials were removed from the filtrate under vacuum conditions. The crude yield was about 90%. Either vacuum distillation or low temperature crystallization is used to purify the end product. 1H NMR (C6D6): δ 0.39 (br, 2H), 1.11 (t, 24H), 2.54 (d, 6H), 3.06 (q, 16H). 3C{1H} NMR (C6D6): δ 14.8 (—CH2CH3), 28.2 (—CH2CH3), 38.3 (—HNCH3). m/z: 332 [M+-(—NEt2)], 202 [M+-(—Si(HNMe)(NEt2)2].
    • EXAMPLE 2 Synthesis of (HNBut)(HNMe)Si—Si(HNMe)(HNBut)2
  • The disilane compound (HNBu[0035] t)2(HNMe)Si—Si(HNMe)(HNBut)2 can be synthesized by reacting (HNBut)2(Cl)Si—Si(Cl)(HNBut)2 with about 2 molar ratio of LiN(H)Me, according to the following equations:
  • (HNBut)2(Cl)Si—Si(Cl)(HNBut)2+2 LiN(H)Me→(HNBut)2(HNMe)Si—Si(HNMe)(HNBut)2+2LiCl
  • Specifically, a 250 mL flask was charged with a solution comprising 100 mL diethyl ether and 200.1 mL (1.6M, 32.2 mmol) of n-butyllithium hexanes solution. 1 gram of H[0036] 2NMe was then bubbled into such solution at 0° C. White precipitate material was formed immediately. Upon completion of this addition, the 250 mL reaction flask was allowed to warm up to room temperature and was stirred for about one hour. Subsequently, 5 grams of (HNBut)2(Cl)Si—Si(Cl)(HNBut)2 (12 mmol) in 40 mL diethyl ether was slowly added into the reaction flask, which was stirred overnight and then refluxed for addition four hours. The mixture was filtered at room temperature. 3.5 grams (72% yield) viscous liquid crude product was obtained after removing the volatiles from the filtrate. The end product is purified by recrystallization from hexanes solution at −25° C., and it has a melting temperature between 34° C. and 38° C. 1H NMR (C6D6): δ 0.38 (br, 2H, H-NMe), 0.99 (br, 4H, H-Nbut), 1.31 (s, 36H), 2.66 (d, 6H), 3.06 (q, 16H). 13C{1H}NMR(C6D6): δ 28.3 (—C(CH3)4), 34.2 (—HNCH3), 49.4 (—C(CH3)3). m/z: 332 [M+-(—HNBut)], 202 [M+-(—Si(HNMe)(HNBut)2].
    • EXAMPLE 3 Synthesis of (HNBut)2(NH2)Si—Si(NH2)(HNBut)2
  • The disilane compound (HNBu[0037] t)2(NH2)Si—Si(NH2)(HNBut)2 can be synthesized by reacting (HNBut)2(Cl)Si—Si(Cl)(HNBut)2 with about 2 molar ratio of LiNH2, according to the following equations:
  • (HNBut)2(Cl)Si—Si(Cl)(HNBut)2+2LiNH2→(HNBut)2(NH2)Si—Si(NH2)(HNBut)2+2LiCl
  • Specifically, a 250 mL flask was charged with a solution comprising 100 mL monoglyme and 5 grams (12.0 mmol) of HNBu[0038] t)2(Cl)Si—Si(Cl)(HNBut)2. 0.58 gram (25.2 mmol) LiNH2 was added and heated to reflux for approximately four hours. All volatile material was removed from the resulting mixture under vacuum. Approximately 150 mL hexanes was used to extract the product. After filtration, the filtrate was concentrated to about 80 mL and stored in a freezer overnight. White crystal material was separated from the solution and dried under vacuum, resulting in about 60% yield. About 20% of such dried crystal material was further recovered in purified form through recrystallization. 1H NMR (C6D6): δ 0.60 (br, 4H), 1.32 (s, 36H). 13C{1H}NMR (C6D6): δ 34.2 (—C(CH3)4), 49.6 (—C(CH3)3). m/z: 232 [M+-(—HNBut)], 188 [M+-(—Si(NH2)(HNBut)2].
  • The disilane derivative compounds of the present invention as described hereinabove can be used, either separately or as mixtures, for low-temperature CVD deposition of various silicon-containing films, including silicon nitride thin films, consistent with the disclosure in U.S. patent application Ser. No. 10/294,431 for “Composition and Method for Low Temperature Deposition of Silicon-Containing Films Including Silicon Nitride, Silicon Dioxide and/or Silicon-Oxynitride” filed on Nov. 14, 2002, the content of which is incorporated by reference in its entirety for all purposes. [0039]
  • Preferably, one or more of the above-described disilane derivatives are first dissolved in a hydrocarbon solvent or a solvent system that comprises at least one hydrocarbon solvent. Suitable hydrocarbon solvents for the practice of the present invention include, but are not limited to, alkylamines such as HN[0040] iPr2, wherein iPr is used herein as the abbreviation of isopropyl. Such solution containing the disilane derivative(s) of the present invention is vaporized at a temperature that is not higher than 300° C., preferably not higher than 150° C., and more preferably about 120° C., and transported to the deposition chamber together with a carrier gas, such as helium or argon, for contact with a heated substrate surface to deposit the silicon-containing thin films.
  • Silicone nitride deposition processes using one or more disilane derivatives of the present invention are described in the following examples: [0041]
    • EXAMPLE 4 Silicon nitride deposition with (HNEt)3Si—Si(HNEt)3 and HNiPr2
  • A solution of the compound (HNEt)[0042] 3Si—Si(HNEt)3 was prepared at a concentration of 0.4M in a hydrocarbon solvent and at a concentration of 0.036M in HNiPr2. These solutions were metered at 0.0127 ml/minute and 0.167 ml/miniute, respectively into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas. The vapor was mixed with 50 sccm or 25 sccm, respectively of NH3 in a showerhead vaporizer device that was maintained at 120° C. and thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at 10 Torr to 60 Torr during deposition. The growth rate of the silicon nitride films ranged from 72 Å/minute to 34 Å/minute depending upon pressure, temperature, NH3 rate, and precursor rate.
  • Chemical analysis of the films, by a combination of RBS (Rutherford Backscattering), HFS (Hydrogen Forward Scattering), and NRA (Nuclear Reaction Analysis), and spectroscopic ellipsometry revealed that (HNEt)[0043] 3Si—Si(HNEt)3 with HNiPr2 deposits films with decreased hydrogen impurity and increased carbon impurity for the same ultra-violet absorption edge (UVAE), deposition rate, and index of refraction as shown in Table 1 below.
    TABLE 1
    Film composition for various deposition conditions using the
    precursor (HNEt)3Si—Si(HNEt)3 with the
    nitrogen source and solvent HNiPr2
    NH3 HNiPr2 T P Rate UVAE H
    (sccm) (sccm) (° C.) (torr) (Å/min) n (eV) (at %) C (at %) N/Si
    25 25 550 20 41 1.92 4.13 16.5 10.8 1.23
    50 0 550 60 44 1.85 4.31 19.0 5.6 1.24
    25 25 550 10 41 1.98 3.91 14.7 11.0 1.10
    50 0 550 20 36 1.94 3.82 15.0 6.9 1.12
    • EXAMPLE 5 Silicon Nitride Deposition with (NEt2)2(HNMe)Si—Si(HNMe)(NEt2)2
  • A solution of the compound of Example 1, (NEt[0044] 2)2(HNMe)Si—Si(HNMe)(NEt2)2, was prepared at a concentration of 0.4M in a hydrocarbon solvent. This solution was metered at 0.0127 ml/minute or 0.025 ml/miniute into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas. The vapor was mixed with 50 sccm or 300 sccm of NH3 in a showerhead vaporizer device that was maintained at 120° C. and thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at 5 Torr to 60 Torr during deposition. The growth rate of the silicon nitride films ranged from 20 Å/minute to 2 Å/minute depending upon pressure, temperature, NH3 rate, and precursor rate.
  • Chemical analysis of the films, by a combination of RBS (Rutherford Backscattering), HFS (Hydrogen Forward Scattering), and NRA (Nuclear Reaction Analysis), and spectroscopic ellipsometry revealed that (NEt[0045] 2)2(HNMe)Si—Si(HNMe)(NEt2)2 deposits films with increased the N/Si ratio along with higher ultra-violet absorption edge (UVAE) and index of refraction and decreased the impurity carbon and hydrogen content as shown in Table 2 below.
    TABLE 2
    Film composition for various deposition conditions using the
    precursor (NEt2)2(HNMe)Si—Si(HNMe)(NEt2)2
    Rate
    NH3 T P (Å/ UVAE H C
    (sccm) (° C.) (torr) min) n (eV) (at %) (at %) N/Si
    300 600 20 8 1.96 5.21 9.5 1.7 1.36
    50 550 5 13 1.99 4.00 10.0 8.5 1.20
    • EXAMPLE 6 Silicon Nitride Deposition with (HNBut)2(HNMe)Si—Si(HNMe)(HNBut)2
  • A solution of the compound of Example 2, (HNBu[0046] t)2(HNMe)Si—Si(HNMe)(HNBut)2, was prepared at a concentration of 0.4M in a hydrocarbon solvent. This solution was metered at 0.0127 ml/minute or 0.025 ml/miniute into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas. The vapor was mixed with 50 sccm or 300 sccm of NH3 in a showerhead vaporizer device that was maintained at 120° C. and thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at 20 Torr to 60 Torr during deposition. The growth rate of the silicon nitride films ranged from 30 Å/minute to 2 Å/minute depending upon pressure, temperature, NH3 rate, and precursor rate.
  • Chemical analysis of the films, by a combination of RBS (Rutherford Backscattering), HFS (Hydrogen Forward Scattering), and NRA (Nuclear Reaction Analysis), and spectroscopic ellipsometry revealed that (HNBu[0047] t)2(HNMe)Si—Si(HNMe)(HNBut)2 deposits films with super-stoichiometric N/Si ratio along with high ultra-violet absorption edge (UVAE) independent of process condition. Index of refraction and the impurity carbon and hydrogen contents were reduced as shown in Table 3 below.
    TABLE 3
    Film composition for various deposition conditions using the
    precursor (HNBut)2(HNMe)Si—Si(HNMe)(HNBut)2
    Rate
    NH3 T P (Å/ UVAE H C
    (sccm) (° C.) (torr) min) n (eV) (at %) (at %) N/Si
    50 550 20 13 1.83 5.14 12.5 6.9 1.47
    • EXAMPLE 7 Silicon Nitride Deposition with (HNBut)2(NH2)Si—Si(NH2)(HNBut)2
  • A solution of the compound of Example 3, (HNBu[0048] t)2(NH2)Si—Si(NH2)(HNBut)2, was prepared at a concentration of 0.4M in a hydrocarbon solvent and at a concentration of 0.072M in HNiPr2. These solutions were metered at 0.0127 ml/minute or 0.025 ml/miniute or 0.05 ml/minute or 0.07 ml/minute into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas. The vapor was mixed with 38 sccm to 300 sccm of NH3 in a showerhead vaporizer device that was maintained at 120° C. and thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at 4 Torr to 60 Torr during deposition. The growth rate of the silicon nitride films ranged from 68 Å/minute to 7 Å/minute depending upon pressure, temperature, NH3 rate, and precursor rate.
  • Chemical analysis of the films, by a combination of RBS (Rutherford Backscattering), HFS (Hydrogen Forward Scattering), and NRA (Nuclear Reaction Analysis), and spectroscopic ellipsometry revealed that (HNBu[0049] t)2(NH2)Si—Si(NH2)(HNBut)2 deposits films with high N/Si ratio along with high ultra-violet absorption edge (UVAE) independent of process condition. Index of refraction and the impurity carbon and hydrogen contents were reduced as shown in Table 4 below.
    TABLE 4
    Film composition for various deposition conditions using the
    precursor (HNBut)2(NH2)Si—Si(NH2)(HNBut)2
    NH3 HNiPr2 T P Rate UVAE H
    (sccm) (sccm) (° C.) (torr) (Å/min) n (eV) (at %) C (at %) N/Si
    38 12 550 20 29 1.83 5.01 15.5 7.4 1.42
    30 0 500 4 14 1.74 5.70 19.5 3.6 1.19
    • EXAMPLE 8 Silicon Nitride Deposition with (HNBut)2(NH)Si—Si(NH2)(HNBut)2 and (HNEt)3Si—Si(HNEt)3
  • A solution of two compounds: 0.0576M (HNBu[0050] t)2(NH2)Si—Si(NH2)(HNBut)2, 0.0144M (HNEt)3Si—Si(HNEt)3 was prepared in HNiPr2. This solution was metered at 0.0138 ml/minute into a vaporizer that was held at temperature of 120° C. and had a flow of 10 standard cubic centimeters per minute (sccm) of He as a carrier gas. The vapor was mixed with 275 sccm of NH3 in a showerhead vaporizer device that was maintained at 120° C. and thereby dispersed over the surface of a heated Si(100) wafer. The chamber pressure was maintained at 10 Torr to 60 Torr during deposition. The growth rate of the silicon nitride films ranged from 33 Å/minute to 7 Å/minute depending upon pressure and temperature.
  • Chemical analysis of the films, by a combination of RBS (Rutherford Backscattering), HFS (Hydrogen Forward Scattering), and NRA (Nuclear Reaction Analysis), and spectroscopic ellipsometry revealed that the combination of (HNBu[0051] t)2(NH2)Si—Si(NH2)(HNBut)2 with (HNEt)3Si—Si(HNEt)3 deposits films whose properties intermediate to those deposited from the two precursors independently. Films with high N/Si ratio along with high ultra-violet absorption edge (UVAE), high index of refraction and very low impurity carbon and hydrogen contents were deposited as shown in Table 5 below.
    TABLE 5
    Film composition for various deposition conditions using the
    precursor (HNBut)2(NH2)Si—Si(NH2)(HNBut)2 with
    (HNEt)3Si—Si(HNEt)3
    NH3 HNiPr2 T P Rate UVAE H
    (sccm) (sccm) (° C.) (torr) (Å/min) n (eV) (at %) C (at %) N/Si
    275 25 550 20 11 1.90 4.86 10.5 3.1 1.42
  • While the invention has been described herein with reference to various specific embodiments, it will be appreciated that the invention is not thus limited, and extends to and encompasses various other modifications and embodiments, as will be appreciated by those ordinarily skilled in the art. Accordingly, the invention is intended to be broadly construed and interpreted, in accordance with the ensuing claims. [0052]

Claims (31)

What is claimed is:
1. A silicon compound comprising a disilane derivative that is fully substituted with alkylamino and/or dialkylamino functional groups.
2. The silicon compound of claim 1, characterized by two or more alkylamino and/or dialkylamino functional groups symmetrically distributed in relation to the Si—Si bond.
3. The silicon compound of claim 1, characterized by two or more alkylamino functional groups symmetrically distributed in relation to the Si—Si bond.
4. The silicon compound of claim 1, characterized by two or more dialkylamino functional groups symmetrically distributed in relation to the Si—Si bond.
5. The silicon compound of claim 1, characterized by a melting temperature of less than 100° C.
6. The silicon compound of claim 1, characterized by a vaporization temperature of less than 300° C.
7. A silicon compound having the formula:
Figure US20040138489A1-20040715-C00003
wherein:
R1-R12 may be the same as or different from one another and each is independently selected from the group consisting of H, C1-C5 alkyl, and C3-C6 cycloalkyl.
8. The silicon compound of claim 7, characterized by two or more alkylamino and/or dialkylamino functional groups symmetrically distributed in relation to the Si—Si bond.
9. The silicon compound of claim 7, characterized by two or more alkylamino functional groups symmetrically distributed in relation to the Si—Si bond.
10. The silicon compound of claim 7, characterized by two or more dialkylamino functional groups symmetrically distributed in relation to the Si—Si bond.
11. The silicon compound of claim 7, characterized by a melting temperature of less than 100° C.
12. The silicon compound of claim 7, characterized by a vaporization temperature of less than 300° C.
13. A silicon compound selected from the group consisting of (NEt2)2(HNMe)Si—Si(HNMe)(NEt2)2, (HNBut)2(HNMe)Si—Si(HNMe)(HNBut)2, and (HNBut)2(NH2)Si—Si(NH2)(HNBut)2.
14. A method for forming a silicon compound as in claim 13, comprising one of the following reactions:
(1) (NEt2)2(Cl)Si—Si(Cl)(NEt2)2+excess H2NMe→(NEt2)2(HNMe)Si—Si(HNMe)(NEt2)2+2H2NMe·HCl;
(2) (HNBut)2(Cl)Si—Si(Cl)(HNBut)2+2 LiN(H)Me→(HNBut)2(HNMe)Si—Si(HNMe)(HNBut)2+2LiCl; and
(3) (HNBut)2(Cl)Si—Si(Cl)(HNBut)2+2LiNH2 →(HNBut)2(NH2)Si—Si(NH2)(HNBut)2+2LiCl.
15. A method of forming a silicon-containing film on a substrate, comprising contacting a substrate under chemical vapor deposition conditions with a vapor of a silicon compound as in claim 1.
16. A method of forming a silicon-containing film on a substrate, comprising contacting a substrate under chemical vapor deposition conditions with a vapor of a silicon compound as in claim 7.
17. A method of forming a silicon-containing film on a substrate, comprising contacting a substrate under chemical vapor deposition conditions with a vapor of a silicon compound as in claim 13.
18. A composition for chemical vapor deposition of a silicon-containing film on a substrate, said composition comprising (i) one ore more disilane derivatives that are fully substituted with alkylamino and/or dialkylamino functional groups and (ii) one or more hydrocarbon solvents.
19. The composition of claim 18, wherein said hydrocarbon solvents comprise HNiPr2.
20. The composition of claim 18, comprising at least two disilane derivatives.
21. A composition for chemical vapor deposition of a silicon-containing film on a substrate, said composition comprising:
(a) one or more silicon compounds having the formula:
Figure US20040138489A1-20040715-C00004
wherein:
R1-R12 may be the same as or different from one another and each is independently selected from the group consisting of H, C1-C5 alkyl, and C3-C6 cycloalkyl; and
(b) one or more hydrocarbon solvents.
22. The composition of claim 21, wherein said hydrocarbon solvents comprise HNiPr2.
23. The composition of claim 21, comprising at least two disilane derivatives.
24. A method of forming a silicon-containing film on a substrate, comprising the steps of:
(a) providing a composition as in claim 18;
(b) vaporizing said composition to form a precursor vapor; and
(c) contacting the substrate under chemical vapor deposition conditions with said precursor vapor to form said silicon-containing film.
25. The method of claim 24, wherein said composition is vaporized at a temperature that is not higher than 300° C.
26. The method of claim 24, wherein said composition is vaporized at a temperature that is not higher than 150° C.
27. The method of claim 24, wherein said silicon-containing film comprises silicon nitride.
28. A method of forming a silicon-containing film on a substrate, comprising the steps of:
(a) providing a composition as in claim 21;
(b) vaporizing said composition to form a precursor vapor; and
(c) contacting the substrate under chemical vapor deposition conditions with said precursor vapor to form said silicon-containing film.
29. The method of claim 28, wherein said composition is vaporized at a temperature that is not higher than 300° C.
30. The method of claim 28, wherein said composition is vaporized at a temperature that is not higher than 150° C.
31. The method of claim 28, wherein said silicon-containing film comprises silicon nitride.
US10/699,079 2002-11-14 2003-10-31 Composition and method for low temperature deposition of silicon-containing films Active 2024-06-11 US7446217B2 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US10/699,079 US7446217B2 (en) 2002-11-14 2003-10-31 Composition and method for low temperature deposition of silicon-containing films
PCT/US2003/036097 WO2004044958A2 (en) 2002-11-14 2003-11-12 Composition and method for low temperature deposition of silicon-containing films
JP2004552143A JP2006517517A (en) 2002-11-14 2003-11-12 Compositions and methods for low temperature deposition of silicon-containing films, such as films comprising silicon, silicon nitride, silicon dioxide and / or silicon oxynitride
EP03781915A EP1567531A4 (en) 2002-11-14 2003-11-12 Composition and method for low temperature deposition of silicon-containing films such as films including silicon, silicon nitride, silicon dioxide and/or silicon-oxynitride
AU2003287710A AU2003287710A1 (en) 2002-11-14 2003-11-12 Composition and method for low temperature deposition of silicon-containing films
US12/247,120 US7713346B2 (en) 2002-11-14 2008-10-07 Composition and method for low temperature deposition of silicon-containing films
US12/777,519 US7887883B2 (en) 2002-11-14 2010-05-11 Composition and method for low temperature deposition of silicon-containing films
US13/028,193 US8236097B2 (en) 2002-11-14 2011-02-15 Composition and method for low temperature deposition of silicon-containing films

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/294,431 US7531679B2 (en) 2002-11-14 2002-11-14 Composition and method for low temperature deposition of silicon-containing films such as films including silicon nitride, silicon dioxide and/or silicon-oxynitride
US10/699,079 US7446217B2 (en) 2002-11-14 2003-10-31 Composition and method for low temperature deposition of silicon-containing films

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US10/294,431 Continuation-In-Part US7531679B2 (en) 2002-11-14 2002-11-14 Composition and method for low temperature deposition of silicon-containing films such as films including silicon nitride, silicon dioxide and/or silicon-oxynitride

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/247,120 Continuation US7713346B2 (en) 2002-11-14 2008-10-07 Composition and method for low temperature deposition of silicon-containing films

Publications (2)

Publication Number Publication Date
US20040138489A1 true US20040138489A1 (en) 2004-07-15
US7446217B2 US7446217B2 (en) 2008-11-04

Family

ID=32314390

Family Applications (4)

Application Number Title Priority Date Filing Date
US10/699,079 Active 2024-06-11 US7446217B2 (en) 2002-11-14 2003-10-31 Composition and method for low temperature deposition of silicon-containing films
US12/247,120 Expired - Lifetime US7713346B2 (en) 2002-11-14 2008-10-07 Composition and method for low temperature deposition of silicon-containing films
US12/777,519 Expired - Lifetime US7887883B2 (en) 2002-11-14 2010-05-11 Composition and method for low temperature deposition of silicon-containing films
US13/028,193 Expired - Fee Related US8236097B2 (en) 2002-11-14 2011-02-15 Composition and method for low temperature deposition of silicon-containing films

Family Applications After (3)

Application Number Title Priority Date Filing Date
US12/247,120 Expired - Lifetime US7713346B2 (en) 2002-11-14 2008-10-07 Composition and method for low temperature deposition of silicon-containing films
US12/777,519 Expired - Lifetime US7887883B2 (en) 2002-11-14 2010-05-11 Composition and method for low temperature deposition of silicon-containing films
US13/028,193 Expired - Fee Related US8236097B2 (en) 2002-11-14 2011-02-15 Composition and method for low temperature deposition of silicon-containing films

Country Status (5)

Country Link
US (4) US7446217B2 (en)
EP (1) EP1567531A4 (en)
JP (1) JP2006517517A (en)
AU (1) AU2003287710A1 (en)
WO (1) WO2004044958A2 (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040096582A1 (en) * 2002-11-14 2004-05-20 Ziyun Wang Composition and method for low temperature deposition of silicon-containing films such as films including silicon nitride, silicon dioxide and/or silicon-oxynitride
US20050227017A1 (en) * 2003-10-31 2005-10-13 Yoshihide Senzaki Low temperature deposition of silicon nitride
WO2007025565A1 (en) * 2005-09-01 2007-03-08 Freescale Semiconductor, Inc. Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and material for coupling a dielectric layer and a metal layer in a semiconductor device
US20080081106A1 (en) * 2006-09-29 2008-04-03 Air Liquide Electronics U.S. Lp Silicon precursors and method for low temperature cvd of silicon-containing films
US20080160174A1 (en) * 2003-10-10 2008-07-03 Advanced Technology Materials, Inc. Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same
US20080207005A1 (en) * 2005-02-15 2008-08-28 Freescale Semiconductor, Inc. Wafer Cleaning After Via-Etching
US20090045164A1 (en) * 2006-02-03 2009-02-19 Freescale Semiconductor, Inc. "universal" barrier cmp slurry for use with low dielectric constant interlayer dielectrics
US20090084288A1 (en) * 2002-11-14 2009-04-02 Advanced Technology Materials, Inc. Composition and method for low temperature deposition of silicon-containing films
US20090115031A1 (en) * 2006-02-23 2009-05-07 Freescale Semiconductor, Inc. Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and passivating coupling material comprising multiple organic components for use in a semiconductor device
US20090301867A1 (en) * 2006-02-24 2009-12-10 Citibank N.A. Integrated system for semiconductor substrate processing using liquid phase metal deposition
US20100068894A1 (en) * 2003-10-10 2010-03-18 Advanced Technology Materials, Inc. Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US20100112211A1 (en) * 2007-04-12 2010-05-06 Advanced Technology Materials, Inc. Zirconium, hafnium, titanium, and silicon precursors for ald/cvd
US20120319169A1 (en) * 2011-06-20 2012-12-20 Imec Cmos compatible method for manufacturing a hemt device and the hemt device thereof
US9443736B2 (en) 2012-05-25 2016-09-13 Entegris, Inc. Silylene compositions and methods of use thereof
US10041167B2 (en) 2015-02-23 2018-08-07 Applied Materials, Inc. Cyclic sequential processes for forming high quality thin films

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4116283B2 (en) 2001-11-30 2008-07-09 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード Hexakis (monohydrocarbylamino) disilane and process for producing the same
US7618837B2 (en) 2004-06-29 2009-11-17 Peking University Method for fabricating high aspect ratio MEMS device with integrated circuit on the same substrate using post-CMOS process
US20060019032A1 (en) * 2004-07-23 2006-01-26 Yaxin Wang Low thermal budget silicon nitride formation for advance transistor fabrication
US8377511B2 (en) 2006-04-03 2013-02-19 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for depositing silicon nitride films and/or silicon oxynitride films by chemical vapor deposition
US8153832B2 (en) 2006-04-03 2012-04-10 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Pentakis(dimethylamino) disilane precursor comprising compound and method for the preparation thereof
WO2008088563A2 (en) * 2007-01-17 2008-07-24 Advanced Technology Materials, Inc. Precursor compositions for ald/cvd of group ii ruthenate thin films
US9337054B2 (en) * 2007-06-28 2016-05-10 Entegris, Inc. Precursors for silicon dioxide gap fill
KR20090068179A (en) 2007-12-21 2009-06-25 에이에스엠 인터내셔널 엔.브이. Process for producing a thin film comprising silicon dioxide
US8298628B2 (en) 2008-06-02 2012-10-30 Air Products And Chemicals, Inc. Low temperature deposition of silicon-containing films
WO2010047869A1 (en) * 2008-10-20 2010-04-29 Dow Corning Corporation Cvd precursors
JP5665289B2 (en) 2008-10-29 2015-02-04 株式会社日立国際電気 Semiconductor device manufacturing method, substrate processing method, and substrate processing apparatus
US8663735B2 (en) * 2009-02-13 2014-03-04 Advanced Technology Materials, Inc. In situ generation of RuO4 for ALD of Ru and Ru related materials
DE102009001181A1 (en) * 2009-02-26 2010-09-02 Wacker Chemie Ag Cyclic aza-silane compounds
US8912353B2 (en) 2010-06-02 2014-12-16 Air Products And Chemicals, Inc. Organoaminosilane precursors and methods for depositing films comprising same
US8771807B2 (en) * 2011-05-24 2014-07-08 Air Products And Chemicals, Inc. Organoaminosilane precursors and methods for making and using same
US20140203270A1 (en) * 2011-09-12 2014-07-24 Nippon Steel & Sumikin Chemical Co., Ltd. Organic electroluminescent element material having silicon-containing four membered ring structure, and organic electroluminescent element
US9978585B2 (en) 2012-06-01 2018-05-22 Versum Materials Us, Llc Organoaminodisilane precursors and methods for depositing films comprising same
US9337018B2 (en) 2012-06-01 2016-05-10 Air Products And Chemicals, Inc. Methods for depositing films with organoaminodisilane precursors
US9824881B2 (en) 2013-03-14 2017-11-21 Asm Ip Holding B.V. Si precursors for deposition of SiN at low temperatures
US9564309B2 (en) 2013-03-14 2017-02-07 Asm Ip Holding B.V. Si precursors for deposition of SiN at low temperatures
US9796739B2 (en) 2013-06-26 2017-10-24 Versum Materials Us, Llc AZA-polysilane precursors and methods for depositing films comprising same
JP6144161B2 (en) * 2013-09-03 2017-06-07 株式会社日本触媒 Silicon nitride film raw material and silicon nitride film obtained from the raw material
CN106029679B (en) * 2014-01-08 2018-10-19 Dnf有限公司 New Cyclodisilazane derivative, preparation method and use its silicon-containing film
JP6340251B2 (en) * 2014-05-30 2018-06-06 東京エレクトロン株式会社 Method for forming SiCN film
US9576792B2 (en) 2014-09-17 2017-02-21 Asm Ip Holding B.V. Deposition of SiN
US9875888B2 (en) 2014-10-03 2018-01-23 Applied Materials, Inc. High temperature silicon oxide atomic layer deposition technology
JP6501560B2 (en) * 2015-03-06 2019-04-17 東京エレクトロン株式会社 Method and apparatus for forming silicon nitride film
JP6345136B2 (en) * 2015-03-06 2018-06-20 東京エレクトロン株式会社 Method and apparatus for forming carbon-containing silicon nitride film
JP2016182537A (en) * 2015-03-25 2016-10-20 宇部興産株式会社 Processing method of 1,2,3-triazole compound
WO2016172192A1 (en) * 2015-04-20 2016-10-27 Applied Materials, Inc. Deposition of si-h free silicon nitride
JP6479560B2 (en) * 2015-05-01 2019-03-06 東京エレクトロン株式会社 Deposition equipment
CN113403604A (en) * 2015-07-31 2021-09-17 弗萨姆材料美国有限责任公司 Compositions and methods for depositing silicon nitride films
US10410857B2 (en) 2015-08-24 2019-09-10 Asm Ip Holding B.V. Formation of SiN thin films
TWI617693B (en) * 2015-12-21 2018-03-11 慧盛材料美國責任有限公司 Compositions and methods using same for deposition of silicon-containing film
TWI724141B (en) 2016-03-23 2021-04-11 法商液態空氣喬治斯克勞帝方法硏究開發股份有限公司 Si-containing film forming compositions and methods of making and using the same
KR102548405B1 (en) * 2017-04-20 2023-06-28 (주)디엔에프 composition for depositing silicon-containing thin film containing a disilylamine compound and method for manufacturing a silicon-containing thin film using the same
JP2018101810A (en) * 2018-03-14 2018-06-28 東京エレクトロン株式会社 DEPOSITION METHOD OF SiCN FILM
US10580645B2 (en) 2018-04-30 2020-03-03 Asm Ip Holding B.V. Plasma enhanced atomic layer deposition (PEALD) of SiN using silicon-hydrohalide precursors
US11107674B2 (en) 2019-01-24 2021-08-31 Applied Materials, Inc. Methods for depositing silicon nitride
JP7065805B2 (en) * 2019-05-13 2022-05-12 大陽日酸株式会社 Halogenated aminosilane compounds, thin film forming compositions and silicon-containing thin films

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013235A (en) * 1999-07-19 2000-01-11 Dow Corning Corporation Conversion of direct process high-boiling residue to monosilanes
US6383955B1 (en) * 1998-02-05 2002-05-07 Asm Japan K.K. Silicone polymer insulation film on semiconductor substrate and method for forming the film
US6936548B2 (en) * 2001-11-30 2005-08-30 L'air Liquide, Societe Anonyme Pour L'etude Et, L'exploitation Des Procedes Georges Claude Method for depositing silicon nitride films and silicon oxynitride films by chemical vapor deposition
US7019159B2 (en) * 2001-11-30 2006-03-28 L'air Liquide Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Hexakis(monohydrocarbylamino) disilanes and method for the preparation thereof

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2678621A1 (en) 1991-07-02 1993-01-08 Atochem PROCESS FOR THE PREPARATION OF BORON NITRIDE CERAMICS AND PRECURSORS THEREOF FROM HYDRAZINE DERIVATIVES AND PRECURSORS THUS IMPLEMENTED THEREBY
US5204141A (en) 1991-09-18 1993-04-20 Air Products And Chemicals, Inc. Deposition of silicon dioxide films at temperatures as low as 100 degree c. by lpcvd using organodisilane sources
FR2693204A1 (en) 1992-08-27 1994-01-07 Atochem Elf Sa Poly:silyl-hydrazine(s) prepn., used as coatings on e.g. ceramics, metals or metalloid(s) - comprises reacting halo-silane(s) or di:silane(s) with hydrazine(s) in presence of inert solvent
US5424095A (en) 1994-03-07 1995-06-13 Eniricerche S.P.A. Ceramic vapor deposited coating using a steam-containing carrier gas and non-alkoxy silane precursors
JPH07335753A (en) 1994-06-06 1995-12-22 Sharp Corp Semiconductor device and its manufacture thereof
JPH0822986A (en) * 1994-07-05 1996-01-23 Sony Corp Method of forming insulating film
JP3282769B2 (en) * 1994-07-12 2002-05-20 ソニー株式会社 Method for manufacturing semiconductor device
TW285753B (en) 1995-01-04 1996-09-11 Air Prod & Chem
US5939333A (en) 1996-05-30 1999-08-17 Micron Technology, Inc. Silicon nitride deposition method
US6365231B2 (en) 1998-06-26 2002-04-02 Kabushiki Kaisha Toshiba Ammonium halide eliminator, chemical vapor deposition system and chemical vapor deposition process
JP2000080476A (en) 1998-06-26 2000-03-21 Toshiba Corp Vapor growth method, vapor growth device and ammonium halide removing device
WO2001066832A2 (en) 2000-03-07 2001-09-13 Asm America, Inc. Graded thin films
US6630413B2 (en) 2000-04-28 2003-10-07 Asm Japan K.K. CVD syntheses of silicon nitride materials
US7132723B2 (en) * 2002-11-14 2006-11-07 Raytheon Company Micro electro-mechanical system device with piezoelectric thin film actuator
US7446217B2 (en) * 2002-11-14 2008-11-04 Advanced Technology Materials, Inc. Composition and method for low temperature deposition of silicon-containing films
US7531679B2 (en) * 2002-11-14 2009-05-12 Advanced Technology Materials, Inc. Composition and method for low temperature deposition of silicon-containing films such as films including silicon nitride, silicon dioxide and/or silicon-oxynitride
US7172792B2 (en) 2002-12-20 2007-02-06 Applied Materials, Inc. Method for forming a high quality low temperature silicon nitride film
US7122222B2 (en) 2003-01-23 2006-10-17 Air Products And Chemicals, Inc. Precursors for depositing silicon containing films and processes thereof
US7601860B2 (en) 2003-10-10 2009-10-13 Advanced Technology Materials, Inc. Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US7579496B2 (en) * 2003-10-10 2009-08-25 Advanced Technology Materials, Inc. Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6383955B1 (en) * 1998-02-05 2002-05-07 Asm Japan K.K. Silicone polymer insulation film on semiconductor substrate and method for forming the film
US6410463B1 (en) * 1998-02-05 2002-06-25 Asm Japan K.K. Method for forming film with low dielectric constant on semiconductor substrate
US6013235A (en) * 1999-07-19 2000-01-11 Dow Corning Corporation Conversion of direct process high-boiling residue to monosilanes
US6936548B2 (en) * 2001-11-30 2005-08-30 L'air Liquide, Societe Anonyme Pour L'etude Et, L'exploitation Des Procedes Georges Claude Method for depositing silicon nitride films and silicon oxynitride films by chemical vapor deposition
US7019159B2 (en) * 2001-11-30 2006-03-28 L'air Liquide Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Hexakis(monohydrocarbylamino) disilanes and method for the preparation thereof

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040096582A1 (en) * 2002-11-14 2004-05-20 Ziyun Wang Composition and method for low temperature deposition of silicon-containing films such as films including silicon nitride, silicon dioxide and/or silicon-oxynitride
US20100285663A1 (en) * 2002-11-14 2010-11-11 Advanced Technology Materials, Inc. Composition and method for low temperature deposition of silicon-containing films such as films including silicon, silicon nitride, silicon dioxide and/or silicon-oxynitride
US7910765B2 (en) 2002-11-14 2011-03-22 Advanced Technology Materials, Inc. Composition and method for low temperature deposition of silicon-containing films such as films including silicon, silicon nitride, silicon dioxide and/or silicon-oxynitride
US7786320B2 (en) 2002-11-14 2010-08-31 Advanced Technology Materials, Inc. Composition and method for low temperature deposition of silicon-containing films such as films including silicon, silicon nitride, silicon dioxide and/or silicon-oxynitride
US7713346B2 (en) 2002-11-14 2010-05-11 Advanced Technology Materials, Inc. Composition and method for low temperature deposition of silicon-containing films
US20090281344A1 (en) * 2002-11-14 2009-11-12 Advanced Technology Materials, Inc. Composition and method for low temperature deposition of silicon-containing films such as films including silicon, silicon nitride, silicon dioxide and/or silicon-oxynitride
US7531679B2 (en) 2002-11-14 2009-05-12 Advanced Technology Materials, Inc. Composition and method for low temperature deposition of silicon-containing films such as films including silicon nitride, silicon dioxide and/or silicon-oxynitride
US20090084288A1 (en) * 2002-11-14 2009-04-02 Advanced Technology Materials, Inc. Composition and method for low temperature deposition of silicon-containing films
US7781605B2 (en) 2003-10-10 2010-08-24 Advanced Technology Materials, Inc. Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US9102693B2 (en) 2003-10-10 2015-08-11 Entegris, Inc. Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US20100068894A1 (en) * 2003-10-10 2010-03-18 Advanced Technology Materials, Inc. Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US8802882B2 (en) 2003-10-10 2014-08-12 Advanced Technology Materials, Inc. Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US20080160174A1 (en) * 2003-10-10 2008-07-03 Advanced Technology Materials, Inc. Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same
US7863203B2 (en) 2003-10-10 2011-01-04 Advanced Technology Materials, Inc. Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same
US9783558B2 (en) 2003-10-10 2017-10-10 Entegris, Inc. Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US20100314590A1 (en) * 2003-10-10 2010-12-16 Advanced Technology Materials, Inc. Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US20050227017A1 (en) * 2003-10-31 2005-10-13 Yoshihide Senzaki Low temperature deposition of silicon nitride
US20080207005A1 (en) * 2005-02-15 2008-08-28 Freescale Semiconductor, Inc. Wafer Cleaning After Via-Etching
WO2007025565A1 (en) * 2005-09-01 2007-03-08 Freescale Semiconductor, Inc. Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and material for coupling a dielectric layer and a metal layer in a semiconductor device
US20090045164A1 (en) * 2006-02-03 2009-02-19 Freescale Semiconductor, Inc. "universal" barrier cmp slurry for use with low dielectric constant interlayer dielectrics
US20090115031A1 (en) * 2006-02-23 2009-05-07 Freescale Semiconductor, Inc. Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and passivating coupling material comprising multiple organic components for use in a semiconductor device
US20090301867A1 (en) * 2006-02-24 2009-12-10 Citibank N.A. Integrated system for semiconductor substrate processing using liquid phase metal deposition
US7803719B2 (en) 2006-02-24 2010-09-28 Freescale Semiconductor, Inc. Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and passivating coupling material comprising multiple organic components for use in a semiconductor device
US20110171381A1 (en) * 2006-09-29 2011-07-14 Air Liquide Electronics U.S. Lp Silicon precursors and method for low temperature cvd of silicon-containing films
US8101788B2 (en) 2006-09-29 2012-01-24 Air Liquide Electronics U.S. Lp Silicon precursors and method for low temperature CVD of silicon-containing films
US8227358B2 (en) 2006-09-29 2012-07-24 Air Liquide Electronics U.S. Lp Silicon precursors and method for low temperature CVD of silicon-containing films
US20080081106A1 (en) * 2006-09-29 2008-04-03 Air Liquide Electronics U.S. Lp Silicon precursors and method for low temperature cvd of silicon-containing films
US20100112211A1 (en) * 2007-04-12 2010-05-06 Advanced Technology Materials, Inc. Zirconium, hafnium, titanium, and silicon precursors for ald/cvd
US9070758B2 (en) * 2011-06-20 2015-06-30 Imec CMOS compatible method for manufacturing a HEMT device and the HEMT device thereof
US20150295076A1 (en) * 2011-06-20 2015-10-15 Imec Cmos compatible method for manufacturing a hemt device and the hemt device thereof
US9252258B2 (en) * 2011-06-20 2016-02-02 Imec CMOS compatible method for manufacturing a HEMT device and the HEMT device thereof
US20120319169A1 (en) * 2011-06-20 2012-12-20 Imec Cmos compatible method for manufacturing a hemt device and the hemt device thereof
US9443736B2 (en) 2012-05-25 2016-09-13 Entegris, Inc. Silylene compositions and methods of use thereof
US10041167B2 (en) 2015-02-23 2018-08-07 Applied Materials, Inc. Cyclic sequential processes for forming high quality thin films

Also Published As

Publication number Publication date
AU2003287710A8 (en) 2004-06-03
US20090084288A1 (en) 2009-04-02
US20110136343A1 (en) 2011-06-09
AU2003287710A1 (en) 2004-06-03
US7446217B2 (en) 2008-11-04
WO2004044958A2 (en) 2004-05-27
US7887883B2 (en) 2011-02-15
WO2004044958A3 (en) 2004-08-26
JP2006517517A (en) 2006-07-27
US8236097B2 (en) 2012-08-07
EP1567531A4 (en) 2008-08-20
US20100221914A1 (en) 2010-09-02
EP1567531A2 (en) 2005-08-31
US7713346B2 (en) 2010-05-11

Similar Documents

Publication Publication Date Title
US7446217B2 (en) Composition and method for low temperature deposition of silicon-containing films
US9783558B2 (en) Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US7910765B2 (en) Composition and method for low temperature deposition of silicon-containing films such as films including silicon, silicon nitride, silicon dioxide and/or silicon-oxynitride
US7863203B2 (en) Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same
JP4824823B2 (en) Aminosilane, precursor for forming silicon-containing film, composition for forming silicon-containing film
EP2154141A2 (en) Precursors for depositing silicon-containing films and methods for making and using same
US20060030724A1 (en) Hexakis(monohydrocarbylamino)disilanes and method for the preparation thereof
US20050048204A1 (en) Method for the fabrication of silicon nitride, silicon oxynitride, and silicon oxide films by chemical vapor deposition
KR102308644B1 (en) Silicon precursor compounds, method of preparing the same, and method of forming silicon-containing films using the same
KR101380317B1 (en) Cyclic aminosilane compounds having excellent affinity towards silicon and metal atoms, preparing method thereof, and its application

Legal Events

Date Code Title Description
AS Assignment

Owner name: ADVANCED TECHNOLOGY MATERIALS, INC., CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WANG, ZIYUN;XU, CHONGYING;BAUM, THOMAS H.;AND OTHERS;REEL/FRAME:014443/0927;SIGNING DATES FROM 20031028 TO 20031104

STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

CC Certificate of correction
FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT, NEW YORK

Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;POCO GRAPHITE, INC.;ATMI, INC.;AND OTHERS;REEL/FRAME:032815/0852

Effective date: 20140430

Owner name: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT, NEW Y

Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;POCO GRAPHITE, INC.;ATMI, INC.;AND OTHERS;REEL/FRAME:032815/0852

Effective date: 20140430

AS Assignment

Owner name: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT, NEW YORK

Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;POCO GRAPHITE, INC.;ATMI, INC.;AND OTHERS;REEL/FRAME:032812/0192

Effective date: 20140430

Owner name: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT, NEW Y

Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;POCO GRAPHITE, INC.;ATMI, INC.;AND OTHERS;REEL/FRAME:032812/0192

Effective date: 20140430

AS Assignment

Owner name: ENTEGRIS, INC., MASSACHUSETTS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ADVANCED TECHNOLOGY MATERIALS, INC.;REEL/FRAME:034894/0025

Effective date: 20150204

FPAY Fee payment

Year of fee payment: 8

AS Assignment

Owner name: ENTEGRIS, INC., MASSACHUSETTS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0032

Effective date: 20181106

Owner name: ATMI PACKAGING, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0032

Effective date: 20181106

Owner name: ATMI, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0032

Effective date: 20181106

Owner name: POCO GRAPHITE, INC., MASSACHUSETTS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0032

Effective date: 20181106

Owner name: ADVANCED TECHNOLOGY MATERIALS, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0032

Effective date: 20181106

Owner name: ATMI PACKAGING, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0151

Effective date: 20181106

Owner name: ENTEGRIS, INC., MASSACHUSETTS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0151

Effective date: 20181106

Owner name: ADVANCED TECHNOLOGY MATERIALS, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0151

Effective date: 20181106

Owner name: ATMI, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0151

Effective date: 20181106

Owner name: POCO GRAPHITE, INC., MASSACHUSETTS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0151

Effective date: 20181106

AS Assignment

Owner name: GOLDMAN SACHS BANK USA, NEW YORK

Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;SAES PURE GAS, INC.;REEL/FRAME:048811/0679

Effective date: 20181106

AS Assignment

Owner name: MORGAN STANLEY SENIOR FUNDING, INC., MARYLAND

Free format text: ASSIGNMENT OF PATENT SECURITY INTEREST RECORDED AT REEL/FRAME 048811/0679;ASSIGNOR:GOLDMAN SACHS BANK USA;REEL/FRAME:050965/0035

Effective date: 20191031

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 12

AS Assignment

Owner name: TRUIST BANK, AS NOTES COLLATERAL AGENT, NORTH CAROLINA

Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;ENTEGRIS GP, INC.;POCO GRAPHITE, INC.;AND OTHERS;REEL/FRAME:060613/0072

Effective date: 20220706